Arylene diamine compounds



Patented Apr. 24, 1945 ARYLENE DIAMINE COMPOUNDS Joseph B. Dickey andJames G. McNally, Rochester, N. Y., assignors to Eastman Kodak Company,Rochester, N. Y., a corporation of New Jersey No Drawing. ApplicationMarch 4, 1943, Serial No. 478,003

6 Claims.

This invention relates to arylene diamine derivatives and tophotographic developers comprising such compounds. This application is acontinuation-in-part of our copending application, Serial No. 301,466,filed October 26, 1939.

It i known that oand p-phenylene diamines and some of theirN-substituted derivatives act as photographic developers. N,N-diethyl-pphenylenediamine is used as a photographic developing agentin color photography.

We have now found new carbalkoxyalkyl, acylalkyl and carbamidoalkylderivatives of oand p-arylenediamines, and have further found that thesederivatives are efficacious photographic developers, the carbamidoalkylderivatives being especially useful owing to their low allergeniccharacteristics.

It is, accordingly, an object of our invention to provide new arylenediamine derivatives and a process for the preparation thereof. A furtherobject; is to provide new photographic developing agents comprisingthese new derivatives. Other objects will become apparent hereinafter.

Our new arylene diamine derivatives can be represented by the followinggeneral formula:

wherein D represents an or p-arylene group, e. g. an 0- or p-phenylenegroup, R represents an alkylene group, e. g. methylene, ethylene,propylene, etc, R represents hydrogen or an alcohol radical, e. g.methyl, ethyl, n-propyl, isopropyl, cyclohexyl, benzyl, B-hydroxyethyl,B- ethoxyethyl, B-acetylethyl, carbethoxy-methyl, furfuryl, etc. and R"represents an alcohol radical such as set forth above under R, or analkoxyl group or an amino group, e. g. a primary amino group (-NHz), asecondary amino group (e. g. C2H5NH-) or a tertiary amino group, e. g.

The compounds of lower molecular weight are the most efiicaciousphotographic developers, e.'g. those in which D represents an 0- orp-phenylene group, in which R represents methylene or ethylene, in whichR represents hydrogen, methyl, ethyl or p-hydroxyethyl and in which R."represents methyl, ethyl, methoxyl, ethoxyl, -NH2, inethylamino,ethylamino or dimethylamino. are generally superior to the o-phenylenecompounds. Of th s group of lower molecular weight compounds, theD-Dhenylene. compounds in which R represents an alcohol radical such asmethyl, ethyl or B-hydroxyethyl are especially useful as photographicdevelopers in color photography.

Our new compounds can be prepared by reducing appropriate azo compounds.The reductions are advantageously efiected by hydrogenation, in thepresence of a nickel catalyst, or by means of sodium hydrosulfite(sodium hyposulfite). Our new compounds can also be prepared by reducingthe appropriate nitroso or nitro compounds. These reductions areadvantageously effected by hydrogenation, in the presence of a nickelcatalyst.

The following examples will serve to illustrate our new arylene diaminederivatives and the manner of preparing the same.

0235 2 a HlN l 4 N (CHzhCO CH1 4 g. of sodium were dissolved in 50 cc.of absolute ethyl alcohol. The resulting solution was added with coolingto 20 cc. of ethyl acetoacetate. To the resulting mixture were added 30g. of N-(p-chloroethyl) -N-ethyl-m-toluidine. The resulting mixture wasstirred and heated on a steam bath under reflux for five hours. Thesodium chloride which formed was removed by filtration. The excessethyl' alcohol and ethyl acetoacetate were removed in vacuo. The residuewas dissolved in a mixture of 10 cc. of acetic acid, 200 cc. of waterand 50 cc. of concentrated hydrochloric acid. Ammonia was added to thesolution, whereupon N-ethyl-N-(fi-keto-n-amyl) m-toluidine separatedout. This m-toluidine derivative was extracted from the reaction mixturewith diethyl ether, the ether extract dried over magnesium sulfate, theether evaporated and the residual m-t'oluidine derivative distilled Thep-phenylene compounds,

extracted from the reaction mixture with diethyl ether, the etherextract dried over magnesium sulfate and the ether evaporated. Theremaining phenylenediamine derivative is a yellow oil which cannot bedistilled without decomposition. The sulfate of the phenylenediaminederivative can be prepared by treating the derivative with anequimolecular proportion of percent sulfuric acid.

Example 2--N -ethyl-N -keto -n butyl) 2 methyl-p-phenylenediaminewrunoocm 20.5 g. of N-ethyl-N-( -keto-n-butyl)-m-toluidine weredissolved in 200 cc. of water and ice containing 6 cc. of sulfuric acid.To the resulting mixture was added the diazonium sulfate prepared from12.7g. of o-chloroaniline. The, azo dye which formed was precipitated byadding sodium acetate until all the mineral acid was neutralized. Theazo dye was filtered off and washed with water. It was charged into ashaking autoclave containing 1 g. of Raney nickel catalyst and 200 cc.of methanol. The azo dye was then reduced at to C. under a hydrogenpressure of 1500 pounds. When two molecular equivalents of hydrogen hadbeen absorbed, the mixture was removed from the autoclave, the catalystfiltered off and the methanol distilled off. The residue was then steamdistilled to remove o-chloroaniline. The residue was then treated with amolecular equivalent of 10 percent sulfuric acid. The resulting sulfateof the phenylenediamine derivative was recrystallized from water, usingactivated charcoal to remove color. The resulting sulfate wasgreyish-white in color.

OCHa

24.9-g. of Ni-i'n-propyl)-N-(' -keto-n-amyl) -mamisidine were dissolvedin 200 cc. of water and ice containing 15 cc. of hydrochloric acid. Thediazonium sulfate from 17.3 g. of sulfanilic acid was added to thesolution with stirring. Coupling was completed by adding sodiumcarbonate until the solution was acid to litmus. Sodium hydrosulfite wasthen added until no further color change took place. Sodium hydroxidewas then added until the mixture was alkaline. The resulting mixture wasextracted immediately with benzene. The benzene extract was treated withanimal charcoal to remove color and then filtered. The benzene solutionwas then concentrated to dryness. The resulting phenylenediaminederivative was treated with an equimolecular proportion of 10 percentsulfuric acid to form the sulfate. The sulfate was recrystallized fromwater. It was a greyish-white solid.

Example 4-N,N-di- (p-acetylethyl) -p-phcnylenediamine cuisine 0cmCHzCUzCOCHx 23.3 g. of di-('yketo-n-butyl) -aniline was coupled with thediazonium sulfate from 17.3 g. of sulfanilic acid as in Example 3. Theresulting azo. dye was reduced with sodium hydrosulfite and thephenylenediamine derivative isolated as in Example 3. The sulfate ofphenylenediamine de rivative was a greyish-white solid.

Example 5-N-(o-hydrorcyethyb N -keto-nbutyl) -p-phenylenediamine cmcmonCHzCIIzC O CH:

21.3 g. of N- (p-hydroxyethyU-N-(' ketobutyl) m-toluidine was coupledwith the diazonium sulfate from 17.3 g. of sulfanilic acid as in Example3. The resulting azo dye was reduced with sodium hydrosulfite and thephenylenediamine derivative isolated as in Example 1. The sulfate of thephenylenediamine was a greyish-white solid.

Example 6-N carbamidomeithyl N methyl-pphenylenediamine CHZCONHZ 20.5 g.of N-methyl-N-phenyl glycineamide were suspended in about cc. of 50percent acetic acid. 32 g. of sulfanilic acid were diazotized in theusual manner using sulfuric acid, and the diazonium sulfate added to theabove suspension. Coupling was completed by adding about 20 g. of sodiumacetate. Then sodium hydrosulfite was added to the mixture until furtheraddition caused no color change. The mixture was cooled and sodiumhydroxide added until the mixture was alkaline. The alkaline mixture wasstood in an ice bath for one hour. The crystals which separated werefiltered off and washed with a little ice water. These crystalsconsisted of a mixture of phenylenediamine derivative and sodiumchloride. The crystals were extracted with ethyl alcohol to remove thephenylenediamine derivative. The alcohol was removed from the alcoholicextract and the resulting phenylenediamine derivative was recrystallizedfrom a methanol-water mixture containing 10 percent by volume ofmethanol. The phenylenediamine derivative melted at 137 to 139 C. Thesulfate of the phenylenediamine derivative is a white solid.

Example 7N -carbamidomethyZ-N -(pi-methoaryethyl) -p-phenylenediamineing mixture was added sodium acetate until the color changed from red toorange. The azo dye formed was salted out of the reaction mixture andthen dissolved in 100 cc. of water. Sodium hydrosulfite was added insmall portions to the water solution to reduce the azo dye. Theresulting solution was filtered and made basic with cold 40 percentaqueous sodium hydroxide. The resulting crystalline precipitate ofphenylenediamine derivative was collected on a filter, washed with alittle ice water and recrystallized from water. The resulting slightlypink crystals melted at 102 to 103 C. The white crystalline sulfate wasprepared by treating the phenylenediamine derivative with anequimolecular proportion of 10 percent sulfuric acid.

Example 8N -carbamidomethyl-N ethyl-2- methyl-p-ph.enylenediamine 4 g.of N-ethyl-N-(m-tolyl) -glycineamide were dissolved in glacial aceticacid (20 cc.) and a paste of diazotized sulfanilic acid prepared as inExample 7 was added. An excess of aqueous so dium acetate was added andthe mixture was allowed to stand until coupling was complete (30minutes). The resulting azo dye was salted out, collected on a filterand washed with a little cold water. The moist dye was stirred into 50cc. of water and sodium hydrosuifite was added until the solution becamecolorless. The solution was then neutralized with potassium carbonateand cooled in ice. The crystalline phenylenediamine derivative whichseparated was filtered off, Washed with water and finally recrystallizedfrom water. It melted at 125 to 126 C. Its sulfate can be prepared bytreating the phenylenediamine derivative with a molecularly equivalentamount of 10 percent sulfuric acid.

Example 9N -ethyZ-N (p-carbdimethylamidoethyl)-2-methyl-p-phenylcnediamine ills 135 g. of N -ethyl-m-toluidine and 120g. of ethyl acrylate were heated together in a shaking autoclave for sixhours at 130 C. The reaction mix ture was cooled and fractionallydistilled to give a good yield of N-ethyl-N-(p-carbethoxyethyl)-m-toluidine. 112 g. of this m-toluidine derivative was charged into ashaking autoclave with 250 cc. of methanol and 40 g, of dimethylamine.The mixture was heated at 150 C. for six hours. When cool, the reactionmixture was concentrated to remove the alcohol. The resulting N- ethyl-Ns-carbdimethylamide) ethyl-m-toluidine was taken up in benzene and thebenzene solution Washed with sodium carbonate. The washedbenzenesolution was dried over magnesium sulfate and the benzeneremoved. 57 g. of this latter m-toluidine derivative were dissolved in500 cc. of ice and water containing 50 cc. of hydrochloric acid. To thissolution was added the diazonium sulfate prepared from 32 g. ofochloroaniline. Coupling was completed by adding sodium acetate untilthe mixture was no longer acid to Congo red. The azo dye was filteredoil, washed free from salts, and placed in Call a shaking autoclave in500 cc. of methanol containing g. of Raney nickel. The azo dye wasreduced at 30 to 50 C. under a hydrogen pressure of 1500 pounds. Whenreduction was complete, the reaction mixture wassteam distilled toremove o-chloroaniline. The residue from the .steam distillation wastreated with 490 cc. of 10 percent sulfuric acid. The resulting mixturewas concentrated under reduced pressure until crystals of the sulfate ofN-ethyl-N-(,S-carbdimethylamide)-ethyl-2-methyl-p-phenylenediamine beganto separate. The mixture containing the crystals was cooled in ice. Thecrystals were filtered off, washed with cold water and dried in the air.The crystals were white and did not have a definite melting point.

In a similar manner, N p-carbamidoethyl) -N- (,e-hydroxyethyl) -2methoxy p phenylenediamine and N-carb p hydroxyethylamide-N-methyl-2-chloro-p-phenylenediamine can be prepared.

Ezample 10N -carbamidomethyl-N-terahydrojurfuryl-Z-methyl-p-phenylenediamine 15.5 g. ofN-tetrahydrofurfuryl-N-(m-tolyl) glycineamide were dissolved in aceticacid. The diazonium sulfate from 15 g. of sulfanillc acid were stirredinto the above acetic acid solution. The resulting mixture was allowedto stand for 15 hours. An equal volume of water was added to themixture. To the diluted mixture was added sodium hydrosulfite until theazo dye was completely reduced. The resulting solution was made alkalinewith 40 per cent aqueous sodium hydroxide and then chilled. The oilyprecipitate of phenylenediamine derivative solidified. It was collectedon a filter, washed with a little water, and recrystallized from watercontaining 10 percent by volume) of methyl alcohol. decolorizing withactivated charcoal. The phenylenediamine derivative, a pinkish,crystalline powder. melted at 128 to 129 c.

Example 11N -ethyl-M-carboxymethyl-Z- methyl-p-phenylenediamineN-ethyl-N-(m-tolyl)-glycine ethyl ester 11.8 g.) were dissolved in 50cc. of dilute hydrochloric acid 1 volume of acid to 4 of water). Thesolution was cooled in ice, and there was added slowly, with agitation,a solution of 4 g. of sodium nitrite in 30 cc. of water. After about 30minutes, a p-nitroso derivative was precipitated by neutralizing theresulting mixture with sodium hydroxide. The p-nitroso derivative wasfiltered oil, washed with water and dried in the air. The p-nitrosoderivative was charged into an autoclave with 50 cc. of methanol and 0.5g. of Raney nickel catalyst. at 40 to 60 C. under a hydrogen pressure of1500 pounds. When hydrogenation was complete the contents of theautoclave were cooled and the catalyst filtered off. To the filtratewere added 1.3 g. of sulfuric acid and the sulfate of thephenylenediamine derivative separated out. It was filtered ofi, washedwith acetone and dried in the air.

CHzCHgCO O CH;

HaN

93 g. of N-(fi-hydroxyethyl) -a-naphthylamine, 60 g. of methyl acrylateand 1 g. of acetic acid were heated at 160 C. in 250 cc. of 1,4-dioxanein a shaking autoclave for 12 hours. The reaction mixture was cooled,removed from the autoclave, and distilled under reduced pressure. TheN-(p-carbmethoxyethyl) -N- (p-hydroxyethyD- a-naphthylamine thusobtained (68 g.) was dissolved in 500 cc. of water and ice containing 30cc. of hydrochloric acid. The diazonium sulfate from 32 g. ofo-chloro-aniline was added to the solution and coupling was completed byneutralizing the mineral acid with sodium acetate. The resulting azo dyewas filtered off, washed free from salts with water and then chargedinto an autoclave with 5 g. of Raney nickel catalyst and 500 cc. ofmethanol. The azo dye was hydrogenated at 60 C. under a hydrogenpressure of 1500 pounds. When reduction was complete, the autoclave wascooled and the contents steam distilled to remove o-chloroaniline andmethyl alcohol. 24.5 g. of sulfuric acid were added to the residue andthe resulting sulfate recrystallized from water. The sulfate is apinkish-white substance of indefinite melting point.

Example 13-N-carbethoxymethyl-N- (p-hydrozvyethyl) -o-phenylened-iamineCH1C O C 2H5 CHzCHaOH 91 g. of N-(o-hydroxyethyl)-o-nitroaniline, '73 g.of ethyl chloroacetate and 50 g. of sodium bicarbonate were heated underreflux with a few crystals of sodium iodide. When carbon dioxide is nolonger evolved, the reaction mixture was cooled, the salt filtered offand the filtrated treated with sodium bicarbonate and 30 g. ofp-toluenesulfonyl chloride to react with unchanged N (B hydroxyethyl) onitroaniline. When all the p-toluenesulfonyl chloride had dissolved, themixture was extracted with 10 percent hydrochloric acid to remove theN-(carbethoxy methyl) N (p hydroxyethyl) o nitroaniline. The resultingaqueous solution of the hydrochloride of the o-nitroaniline derivativewas treated with sodium bicarbonate and extracted with ether to obtainthe free o-nitroaniline derivative. The resulting ether solution waswashed with water, and then charged into a shaking autoclave with 5 g.of Raney nickel catalyst. Hydrogenation was carried out at 50 C. under ahydrogen pressure of 1500 pounds. When reduction was complete, theautoclave was cooled, the catalyst filtered off, the ether removed, andthe residue treated with percent sulfuric acid to form the sulfate ofthe phenylenediamine derivative.

Example 14-N -(carbmeth0xymethyl) N (npropyl)-2-methory-p-phenylenediamine O C Hi c zCHzCHa CHzCOOCHl 118 g. ofN-(m-methoxyphenyl) -N-'(n-propyl) glycine methyl ester were dissolvedin dilute hydrochloric acid. The solution was cooled in ice and thediazonium sulfate from 64 g. of o-chloroaniline was added to thesolution. Coupling was completed by neutralizing the mineral acid withsodium acetate. The resulting azo dye was filtered off, washed free fromsalts with water and then charged into an autoclave with 5 g. of Raneynickel catalyst and 500 cc. of methanol. The azo dye was hydrogenated at60 C. under a hydrogen pressure of 1500 pounds. When reduction wascomplete, the autoclave was cooled and the contents steam distilled toremove o-chloroaniline and methyl alcohol. Sulfuric acid was added tothe residue and the resulting sulfate of the phenylenediamine derivativewas recrystallized from water.

Our new arylene diamine derivative can be used to form photographicimages by development of exposed silver halide contained in the usualgelatin carriers, or in carriers, such as collodion, cellulose esters orresins. Those of our new phenylenediamine derivatives which areespecially adapted to use in color photography (see above) can be usedto develop visible images from latent images in silver halide emulsions,or to develop silver images from silver halide images which are obtainedby a so-called reversal process or by rehalogenizing a visible silverimage. When employed in connection with color photography, thephenylenediamine derivatives act as developers in the presence ofcouplers, and the oxidation products of the phenylenediaminederivatives, arising from the developing action, couple with thecouplers or color-formers to give colored bodies or dyes. When used forthe formation of colored photographic images, the phenylenediaminederivatives can be used in conjunction with any well known couplercompounds, such as those described in Fischer U. S, Patent 1,102,028,dated June 30, 1914; Mannes and Godowsky U. S. Patent 2,108,602, datedFebruary 15, 1938; Mannes, Godowsky, and Peterson U. S. Patent2,115,934, dated April 6, 1938, and Mannes, Godowsky, and Peterson U. S.Patent 2,126,337, dated August 9, 1938.

All the arylenediamine derivatives described herein can be used for thepurpose of producing black-and-white images from exposed photographicsilver halide emulsions. Developing solutions comprising our newarylenediamine dirivatives can be made up in the usual manner, usingsodium sulfite and sodium carbonate.

The N- (p-chloroethyl) -N ethyl m toluidine employed in Example 1 wasprepared by condensing N-ethyl-m-toluidine with 1-chloro-2- bromoethane,according to the process described by v. Braun and Kirschbaum in Ber.52, 1716 (1919) for the preparation of N-(fi-chloroethyl) N-metlmlaniline.

The N-ethyl-N-('y-keto-n-butyl) m toluidine employed in Example 2 wasprepared as follows: 107 g. of m-toluidine, '17 g. of methyl vinylketone and 700 g. of water were warmed to 60 C. with stirring. Thereaction mixture was stirred at 60 C. for 10 hours and then fractionallydistilled to give a good yield of N-(v-keto-n-butyl) m-toluidine,boiling at 144 to 148 C. at 4 mm. of mercury pressure. g. of thism-toluidine derivative were mixed with 50 g. of sodium bicarbonate andthe mixture was heated on a steam bath under reflux with g. of ethyliodide for 5 hours. The cool reaction mixture was then extracted with200 cc. of methanol. The methanol was removed from the methanoLextractand the residue distilled under reduced pressure to give a good yield ofN-ethyl-N-(' -keto-n-butyl)-mtoluidine.

The N (n-propyl) -N-'y-keton-amyl) -m-anisidine employed in Example 3was prepared by interacting m-anisidine with ethyl vinyl ketone (exactlyas described above for m-toluidine and methyl vinyl ketone), and theninteracting the so-prepared m-anisidine derivative with n-propropylbromide (exactly as described above for ethyl iodide and the m-toluidinederivative);

The N,N-di-(v-keto-n-butyl) -aniline employed in Example 4 was preparedas follows: 80 g. of N-(y-keto-n-butyD-aniline (prepared by interactingmethyl vinyl ketone and aniline exactly as described above for methylvinyl ketone and m-toluidine) were treated on a steam bath with 60 g. ofB-chloroethyl methyl ketone and 60 g. of sodium bicarbonate. When carbondioxide was no longer evolved, the cool reaction mixture was extractedwith 200 cc. of methanol. The methanol was removed from themethanol-extract and the residue was distilled under reduced pressure toobtain the N,N-di-(' -keto-n-butyl) -aniline.

The N-methyl-N-phenyl glycine amide employed in Example 6 was preparedby interacting N-methylaniline with chlor-acetamide, as described bySilberstein in Ber. 17, 2663 (1884).

N 3 methoxyethyl) N (m-tolyl). glycine amide employed in Example 7 wasprepared by interacting N ,e-methoxyethyl) -m-toluidine withchloracetamide exactly as described by Silberstein for methylaniline andchloracetamide. N- (p-methoxyethyl)-m-toluidine was prepared as follows:107 g. of m-toluidine, g. of Raney nickel catalyst and 160 g. of,e-methoxyethanol were heated, with shaking, in an autoclave, at 220 to240 C. for 40 hours. The reaction product was removed from the cooledautoclave, the catalyst filtered oil and the filtrate fractionallydistilled to give a good yield of N -(p-methoxyethyl) m-toluidine.

N-ethyl-N-(m-tolyl)-glycine amide employed in Example 8 was prepared byinteracting N- ethyl-m-toluidine with chloracetamide exactly asdescribed by Silberstein (supra) for methylaniline and chloracetamide.

N-tetrahydrofurfuryl N (m tolyl) glycineamide employed in Example 10 wasprepared by interacting N -tetrahydrofurfuryl-m-toluidine andchloracetamide exactly as described by Silberstein (supra) formethylaniline and chloracetamide.

N-ethyl-N-(m-tolyl)-glycine ethyl ester employed in Example 11 wasprepared by heating -ethyl-m-toluidine with ethyl chloracetate exactlyas described by Gault, Compt. rend. 145, 126 (1907) for methylanilineand ethyl chloracetate. boils at 162 to 166 C. at 16 mm. of mercurypressure.

N- (m-methoxyphenyl) -N-(n propyl) glycine ethyl ester employed inExample 14 wa prepared by heating N -(npropyl) -m-anisidine with ethylchloracetate exactly as described by Gault N-ethyl-N-(m-tolyl)-glycineethyl ester (supra) for methylaniline and ethyl chloracetate- The term"alcohol radical," in accordance with customary usage, is intended tomean an organic radical which corresponds to an alcohol and is derivedtherefrom by dropping the hydroxyl group, e. g. n-propyl is derived fromn-propyl alcohol by dropping the OH group, benzyl is derived from benzylalcohol by dropping the OH group, and tertiary butyl is derived bydropping the OH group from tertiary butyl alcohol.

What we claim as our invention and desire to be secured by LettersPatent of the United States is:

1. An arylenediamine compound of the following general formula:

R H2N-DN/ \RCOR wherein D represents a p-phenylene group, R representsan alkylene group, R represents an alcohol radical and R" represents anamino group.

2. An arylenediamine compound of the following general formula:

C HaC ON Hg wherein R represents an alcohol radical.

3. An arylenediamine compound of the following general formula:

G C H: C ON H:

CHzC ONHz 5. An arylenediamine compound of the following formula:

CHzCHzOCH:

JOSEPH B. DICKEY. JAMES G. MCNALLY.

CHzCONHa

